JP2001246230A - Exhaust gas treatment method - Google Patents
Exhaust gas treatment methodInfo
- Publication number
- JP2001246230A JP2001246230A JP2000063863A JP2000063863A JP2001246230A JP 2001246230 A JP2001246230 A JP 2001246230A JP 2000063863 A JP2000063863 A JP 2000063863A JP 2000063863 A JP2000063863 A JP 2000063863A JP 2001246230 A JP2001246230 A JP 2001246230A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- stage
- halogen compound
- stage catalyst
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機ハロゲン化合
物を含有する排ガス、または、無機ハロゲン化合物と有
機物とを含有する排ガスを処理する方法に関する。The present invention relates to a method for treating an exhaust gas containing an organic halogen compound or an exhaust gas containing an inorganic halogen compound and an organic substance.
【０００２】[0002]
【従来の技術】有機ハロゲン化合物製造設備からの排ガ
スや各種産業プロセスから排出される有機ハロゲン化合
物には、塩化ビニルモノマー（ＶＣＭ）、クロロホル
ム、トリクロロエチレン、テトラクロロエチレン、ジク
ロロエチレン、塩化メチレン、塩化ビニリデン、クロロ
トルエン、クロロベンゼン、クロロフェノール等の有機
塩素化合物、あるいは臭化メチル、ブロモホルム、臭化
メチレン、臭化エチレン等の有機臭素化合物が含有され
ており、有害な発ガン性物質などが多く含まれている。2. Description of the Related Art Exhaust gas from organic halogen compound production equipment and organic halogen compounds discharged from various industrial processes include vinyl chloride monomer (VCM), chloroform, trichloroethylene, tetrachloroethylene, dichloroethylene, methylene chloride, vinylidene chloride, and chlorotoluene. And organic chlorine compounds such as chlorobenzene, chlorophenol and the like, or organic bromine compounds such as methyl bromide, bromoform, methylene bromide and ethylene bromide, and contain many harmful carcinogenic substances.
【０００３】また、有機ハロゲン化合物が含まれていな
い場合であっても、無機ハロゲン化合物と有機物を含む
各種産業プロセスからの排ガスは処理中に有機ハロゲン
化合物、特に微量であっても極めて有毒なダイオキシン
類を生成する場合がある。したがって、有機ハロゲン化
合物製造設備からの排ガスや各種産業プロセスからの排
ガスを効率良く処理するとともに、ダイオキシン類や一
酸化炭素等の有害な副生成物、特にダイオキシン類の発
生を抑制する技術が早急に求められている。従来から触
媒を用いてこれら排ガスを処理する方法が知られてい
る。Even when no organic halogen compound is contained, exhaust gases from various industrial processes containing an inorganic halogen compound and an organic substance are treated with an organic halogen compound, particularly a very small amount of extremely toxic dioxin during treatment. May be generated. Therefore, technologies to efficiently treat exhaust gas from organic halogen compound production equipment and exhaust gas from various industrial processes and to suppress the generation of harmful by-products such as dioxins and carbon monoxide, particularly dioxins, are urgently required. It has been demanded. Conventionally, a method of treating these exhaust gases using a catalyst has been known.
【０００４】例えば、特開平９−２３９２４１号公報で
は、チタニアとシリカとタングステンを含有し、チタニ
アの表面がシリカ、酸化タングステンの多孔質層で覆わ
れている触媒を、有機ハロゲン化合物を含むガス流と５
００℃を超えない温度で水蒸気の存在下で接触させて、
有機ハロゲン化合物を一酸化炭素、二酸化炭素、ハロゲ
ン化水素に分解する方法が開示されている。しかしこの
触媒を用いた場合、一酸化炭素が生成し、また微量でも
有害なダイオキシン類等が副生成物として生成する可能
性があるが、その処理方法についての記載は見受けられ
ない。特公平６−８７９５０号公報には、炭化水素、ハ
ロゲン化水素および一酸化炭素を含有する塩化ビニル合
成プロセスからの排ガスを触媒を用いて処理する方法が
記載されている。この方法は各種成分が高濃度の場合、
触媒に対する熱的負荷を考慮し触媒を２段にして、第一
帯域の触媒で部分的反応を、第二帯域の触媒で完全酸化
することを目的としている。このように触媒を２段にす
ることにより熱的負荷を分散させているが、第二帯域後
のガス中にも微量でも有害なダイオキシン類等が副生成
物として生成する可能性があり、その処理方法について
は一切記載されていない。[0004] For example, Japanese Patent Application Laid-Open No. 9-239241 discloses a catalyst containing titania, silica and tungsten, the surface of which is covered with a porous layer of silica and tungsten oxide. And 5
Contacting in the presence of steam at a temperature not exceeding 00 ° C.
A method for decomposing an organic halogen compound into carbon monoxide, carbon dioxide, and hydrogen halide is disclosed. However, when this catalyst is used, carbon monoxide may be produced, and harmful dioxins and the like may be produced as by-products even in a very small amount, but there is no description of the treatment method. Japanese Patent Publication No. Hei 6-87950 describes a method for treating an exhaust gas from a vinyl chloride synthesis process containing a hydrocarbon, hydrogen halide and carbon monoxide using a catalyst. This method is used when the concentration of various components is high.
The purpose of the present invention is to provide a two-stage catalyst in consideration of the thermal load on the catalyst, and to partially oxidize the partial reaction with the catalyst in the first zone and completely oxidize with the catalyst in the second zone. As described above, the thermal load is dispersed by using two stages of the catalyst, but harmful dioxins and the like may be generated as by-products even in a trace amount in the gas after the second zone. No treatment method is described.
【０００５】このように従来の方法では有機ハロゲン化
合物製造設備からの排ガスや各種産業プロセスからの排
ガスを効率良く処理するとともに、ダイオキシン類や一
酸化炭素等の有害な副生成物、特にダイオキシン類の発
生を抑制することは不可能であった。As described above, the conventional method efficiently treats exhaust gas from an organic halogen compound manufacturing facility and exhaust gas from various industrial processes, and also removes harmful by-products such as dioxins and carbon monoxide, especially dioxins. It was impossible to control the occurrence.
【０００６】[0006]
【発明が解決しようとする課題】したがって、本発明の
課題は、有機ハロゲン化合物を含有する排ガス、また
は、無機ハロゲン化合物と有機物とを含有する排ガスを
処理するに際し、排ガス中に含まれる有機ハロゲン化合
物や有機物を効率良く処理するとともに、副生成物、特
にダイオキシン類を充分に低減する方法を提供すること
にある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to treat an exhaust gas containing an organic halogen compound or an exhaust gas containing an inorganic halogen compound and an organic substance in treating the exhaust gas containing the organic halogen compound. Another object of the present invention is to provide a method for efficiently treating organic and organic substances and sufficiently reducing by-products, especially dioxins.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するた
め、本発明の排ガスの処理方法は、有機ハロゲン化合物
を含有する排ガス、または、無機ハロゲン化合物と有機
物とを含有する排ガスを処理する方法において、ガス流
れ方向に、前段触媒と後段触媒を配置し、後段触媒層の
入口温度を３００℃以下とすることを特徴とする。ま
た、ガス流れ方向に、前段触媒として有機ハロゲン化合
物分解触媒を、後段触媒としてダイオキシン分解触媒を
配置することを特徴とする。In order to solve the above-mentioned problems, a method for treating exhaust gas according to the present invention is directed to a method for treating exhaust gas containing an organic halogen compound or exhaust gas containing an inorganic halogen compound and an organic substance. The first and second catalysts are arranged in the gas flow direction, and the inlet temperature of the second catalyst layer is set to 300 ° C. or less. Further, in the gas flow direction, an organic halogen compound decomposition catalyst is disposed as a first-stage catalyst, and a dioxin decomposition catalyst is disposed as a second-stage catalyst.
【０００８】[0008]
【発明の実施の形態】本発明では、ガス流れ方向に、前
段触媒と後段触媒を配置する。前段と後段とを分けるこ
とで、用いる触媒や反応温度や空間速度等の処理条件を
別々に設定できるため、それぞれにおいて適切な処理条
件を選択することにより処理効率が向上する。本発明の
好ましい態様を簡単に述べれば、前段は有機ハロゲン化
合物全般の除去を目的として、完全酸化させるべく、比
較的高温で激しく反応させる。後段は前段で生成したダ
イオキシン類の除去を目的として、比較的低温の穏やか
な条件下で処理を行う。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a first-stage catalyst and a second-stage catalyst are arranged in a gas flow direction. By separating the former stage and the latter stage, the processing conditions such as the catalyst to be used, the reaction temperature and the space velocity can be set separately, so that the processing efficiency can be improved by selecting appropriate processing conditions for each. Briefly describing a preferred embodiment of the present invention, in the first stage, the reaction is carried out vigorously at a relatively high temperature in order to completely oxidize the organic halogen compound in order to remove the entire organic halogen compound. In the latter stage, the treatment is performed under relatively low temperature and mild conditions for the purpose of removing dioxins generated in the former stage.
【０００９】本発明では、前段触媒として有機ハロゲン
化合物分解触媒を、後段触媒としてダイオキシン分解触
媒を配置することが好ましい。これにより、有機ハロゲ
ン化合物を効率良く除去でき、また、ダイオキシン類の
発生を抑制することが可能となる。前段触媒として用い
られる有機ハロゲン化合物分解触媒としては、各種有機
ハロゲン化合物を分解しうる触媒であれば特に限定され
ないが、Ａ成分として、Ａｌ、Ｔｉ、Ｓｉ、Ｚｒ、Ｃｅ
およびＷから選ばれる少なくとも１種の元素の酸化物
を、Ｂ成分として、Ｖ、Ｃｕ、Ｃｒ、Ｍｎ、Ｐｄ、Ｒ
ｈ、Ｐｔ、Ｒｕから選ばれる少なくとも１種の元素の金
属または酸化物を含有するものが好ましい。Ｂ成分とし
ては、特にＶ、Ｃｕ、Ｃｒ、Ｍｎから選ばれる少なくと
も１種の元素の金属または酸化物および／またはＰｄ、
Ｒｈ、Ｐｔ、Ｒｕから選ばれる少なくとも１種の元素の
金属または酸化物を含有するものが好ましい。In the present invention, it is preferable to dispose an organic halogen compound decomposing catalyst as a first-stage catalyst and a dioxin decomposing catalyst as a second-stage catalyst. Thereby, the organic halogen compound can be efficiently removed, and the generation of dioxins can be suppressed. The organic halogen compound decomposition catalyst used as the first stage catalyst is not particularly limited as long as it is a catalyst that can decompose various organic halogen compounds, but as the A component, Al, Ti, Si, Zr, Ce
And an oxide of at least one element selected from W and W as V component, V, Cu, Cr, Mn, Pd, R
Those containing a metal or oxide of at least one element selected from h, Pt, and Ru are preferable. As the B component, in particular, a metal or oxide of at least one element selected from V, Cu, Cr, and Mn and / or Pd,
A material containing a metal or oxide of at least one element selected from Rh, Pt, and Ru is preferable.
【００１０】後段触媒として用いられるダイオキシン分
解触媒としては、ダイオキシン類を分解しうる触媒であ
れば特に限定されないが、Ｔｉ、Ｗ、ＭｏおよびＶから
選ばれる少なくとも１種の元素の酸化物を含有するもの
が好ましい。前段触媒、後段触媒とも、形状は特に限定
されるものではなく、ハニカム状、板状、波板状、網
状、円柱状、円筒状など所望の形状に成形して使用する
ことができる。また、アルミナ、シリカ、コージェライ
ト、ムライト、ＳｉＣ、チタニア、ステンレス金属など
からなるハニカム状、板状、波板状、網状、円柱状、円
筒状などの所望の形状の担体に担持して使用してもよ
い。The dioxin decomposition catalyst used as the latter catalyst is not particularly limited as long as it is a catalyst capable of decomposing dioxins, and contains an oxide of at least one element selected from Ti, W, Mo and V. Are preferred. The shape of the first-stage catalyst and the second-stage catalyst is not particularly limited, and they can be used after being formed into a desired shape such as a honeycomb shape, a plate shape, a corrugated plate shape, a net shape, a columnar shape, and a cylindrical shape. Further, it is used by being supported on a carrier having a desired shape such as a honeycomb shape, a plate shape, a corrugated shape, a net shape, a column shape, and a cylindrical shape made of alumina, silica, cordierite, mullite, SiC, titania, stainless steel, or the like. You may.
【００１１】本発明における前段の処理条件としては、
前段触媒層の入口温度を１５０〜５００℃とすることが
好ましく、２００〜４５０℃とすることがより好まし
い。前段触媒層の入口温度が１５０℃を下回る場合に
は、比較的難分解性の有機ハロゲン化合物の処理が困難
となる。一方、５００℃を上回る場合には、助燃剤等が
増加し、経済的でなくなり、また、Ｃｌ2発生量が増加
し、処理装置の損傷につながる。また、前段の空間速度
を５００〜５０，０００ｈｒ-1とすることが好ましく、
１０００〜３０，０００ｈｒ-1とすることがより好まし
い。前段の空間速度が５００ｈｒ-1を下回る場合には、
処理装置が大きくなりすぎ、非効率的となる。一方、５
０，０００ｈｒ-1を上回る場合には、比較的難分解性の
有機ハロゲン化合物の処理が困難となる。In the present invention, the preceding processing conditions include:
The inlet temperature of the former catalyst layer is preferably set to 150 to 500C, more preferably 200 to 450C. When the inlet temperature of the former catalyst layer is lower than 150 ° C., it becomes difficult to treat a relatively hardly decomposable organic halogen compound. On the other hand, when the temperature exceeds 500 ° C., the amount of the auxiliary agent and the like increases, which is not economical, and the amount of Cl 2 generated increases, leading to damage to the processing equipment. Further, it is preferable that the space velocity in the former stage is 500 to 50,000 hr -1 ,
More preferably, it is 1000 to 30,000 hr -1 . If the previous space velocity is below 500 hr -1 ,
Processing equipment becomes too large and inefficient. 5
When it is more than 000 hr −1 , it is difficult to treat a relatively hardly decomposable organic halogen compound.
【００１２】一方、後段の処理条件としては、後段触媒
層の入口温度を３００℃以下とすることが特に好まし
い。排ガス中の有機ハロゲン化合物を前段触媒で処理し
た際にＨＣｌやＣｌ2等が発生した場合、または排ガス
中にＨＣｌやＣｌ2等が含まれる場合は、後段触媒層の
入口温度を３００℃以下とすることで、触媒上でのダイ
オキシン類の再合成を抑制することができる。ただし、
前段触媒として有機ハロゲン化合物分解触媒を、後段触
媒としてダイオキシン分解触媒を配置した場合は、それ
によって有機ハロゲン化合物を効率良く除去でき、また
ダイオキシン類の発生を抑制することが可能となるた
め、後段触媒層の入口温度を必ずしも３００℃以下とす
る必要はなく、例えば１００〜５００℃、好ましくは１
００〜４００℃とすることができる。５００℃を上回る
場合には、触媒の寿命低下につながる可能性があるため
である。しかしながら、この場合においても、後段触媒
層の入口温度を３００℃以下とすることで、触媒上での
ダイオキシン類の再合成を抑制することが可能であるた
め、さらに高い効果を得ることができるのはもちろんの
ことである。On the other hand, it is particularly preferable that the inlet temperature of the latter catalyst layer is set to 300 ° C. or less as the latter treatment condition. When HCl or Cl 2 or the like is generated when the organic halogen compound in the exhaust gas is treated with the first-stage catalyst, or when HCl or Cl 2 or the like is contained in the exhaust gas, the inlet temperature of the second-stage catalyst layer is set to 300 ° C. or less. By doing so, resynthesis of dioxins on the catalyst can be suppressed. However,
When an organic halogen compound decomposition catalyst is disposed as the first catalyst and a dioxin decomposition catalyst is disposed as the second catalyst, the organic halogen compound can be removed efficiently and the generation of dioxins can be suppressed. The inlet temperature of the layer is not necessarily required to be 300 ° C. or lower, for example, 100 to 500 ° C., preferably 1 to 500 ° C.
The temperature can be set to 00 to 400 ° C. If the temperature exceeds 500 ° C., the life of the catalyst may be shortened. However, even in this case, by setting the inlet temperature of the second-stage catalyst layer to 300 ° C. or lower, it is possible to suppress resynthesis of dioxins on the catalyst, so that a higher effect can be obtained. Of course.
【００１３】以上から、後段触媒層の入口温度は３００
℃以下が好ましく、１００〜３００℃がより好ましく、
１３０〜３００℃とすることが最も好ましい。後段触媒
層の入口温度が１００℃を下回る場合には、ダイオキシ
ン類の除去が困難となる。また、後段の空間速度は２０
０〜５０，０００ｈｒ-1とすることが好ましく、５００
〜３０，０００ｈｒ-1とすることがより好ましい。後段
の空間速度が２００ｈｒ-1を下回る場合には、処理装置
が大きくなりすぎ、非効率的となる。一方、５０，００
０ｈｒ-1を上回る場合には、ダイオキシン類の除去が困
難となる。前段触媒と後段触媒とは、同一の反応器に直
列に配列しても良いが、前段触媒と後段触媒を別々の反
応器に充填することが好ましく、さらに、前段反応器と
後段反応器との間に熱交換器を設置して、前段反応器に
おいて発生した熱を除去することがより好ましい。前段
反応器において発生した熱を除去しないで後段触媒によ
る処理を行うと、後段触媒層入口温度が高くなりすぎ
て、後段触媒の物性変化により活性低下や寿命低下が起
こりやすくなるためである。From the above, the inlet temperature of the latter catalyst layer is 300
° C. or less, more preferably 100 to 300 ° C.,
Most preferably, the temperature is set to 130 to 300 ° C. When the inlet temperature of the latter catalyst layer is lower than 100 ° C., it becomes difficult to remove dioxins. The space velocity in the latter stage is 20
0 to 50,000 hr -1 , preferably 500
More preferably, it is set to ３０30,000 hr −1 . If the downstream space velocity is less than 200 hr -1 , the processing device becomes too large and inefficient. On the other hand, 50,000
If it exceeds 0 hr −1 , it becomes difficult to remove dioxins. Although the first-stage catalyst and the second-stage catalyst may be arranged in series in the same reactor, it is preferable that the first-stage catalyst and the second-stage catalyst are filled in separate reactors. It is more preferable to install a heat exchanger in between to remove heat generated in the pre-stage reactor. This is because if the treatment with the second-stage catalyst is performed without removing the heat generated in the first-stage reactor, the inlet temperature of the second-stage catalyst layer becomes too high, and the activity and life of the second-stage catalyst are likely to decrease due to a change in the physical properties of the second-stage catalyst.
【００１４】本発明の処理対象となる排ガスは、有機ハ
ロゲン化合物を含有する排ガス、または、無機ハロゲン
化合物と有機物とを含有する排ガスである。前記有機ハ
ロゲン化合物としては、塩化ビニルモノマー、クロロホ
ルム、トリクロロエチレン、テトラクロロエチレン、ジ
クロロエチレン、塩化メチレン、塩化ビニリデン、クロ
ロトルエン、クロロベンゼン、クロロフェノール等の有
機塩素化合物；あるいは臭化メチル、ブロモホルム、臭
化メチレン、臭化エチレン等の有機臭素化合物等が挙げ
られる。前記無機ハロゲン化合物としては、ＨＣｌ、Ｃ
ｌ2、ＨＢｒ、Ｂｒ2等が挙げられる。前記有機物として
は、有機ハロゲン化合物の他、エタン、プロパン、ブタ
ン等の飽和炭化水素；エチレン、プロピレン、ブテン等
の不飽和炭化水素；シクロヘキサン、シクロヘキセン、
シクロペンタン等の脂環式炭化水素；メタノール、エタ
ノール、プロパノール等のアルコール類；ホルムアルデ
ヒド、アセトアルデヒド、ブチルアルデヒド等のアルデ
ヒド類；アセトン、メチルエチルケトン、メチルイソブ
チルケトン等のケトン類；メチルエーテル、エチルエー
テル等のエーテル類；酢酸メチル、酢酸エチル、酢酸ブ
チル等のエステル類；ベンゼン、トルエン、キシレン、
スチレン、フェノール、クメン等の芳香族化合物；ギ
酸、酢酸、フタル酸、マレイン酸等の有機酸；アセトニ
トリル、アクリロニトリル、トリメチルアミン、トリエ
チルアミン、アニリン、ピリジン等の含窒素化合物等が
挙げられる。The exhaust gas to be treated in the present invention is an exhaust gas containing an organic halogen compound or an exhaust gas containing an inorganic halogen compound and an organic substance. Examples of the organic halogen compounds include vinyl chloride monomers, chloroform, trichloroethylene, tetrachloroethylene, dichloroethylene, methylene chloride, vinylidene chloride, chlorotoluene, chlorobenzene, chlorophenol, and other organic chlorine compounds; or methyl bromide, bromoform, methylene bromide, And organic bromine compounds such as ethylene chloride. As the inorganic halogen compound, HCl, C
l 2 , HBr, Br 2 and the like. Examples of the organic substance include, in addition to organic halogen compounds, saturated hydrocarbons such as ethane, propane, and butane; unsaturated hydrocarbons such as ethylene, propylene, and butene; cyclohexane, cyclohexene,
Alicyclic hydrocarbons such as cyclopentane; alcohols such as methanol, ethanol and propanol; aldehydes such as formaldehyde, acetaldehyde and butyl aldehyde; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl ether and ethyl ether Ethers; esters such as methyl acetate, ethyl acetate, and butyl acetate; benzene, toluene, xylene,
Aromatic compounds such as styrene, phenol and cumene; organic acids such as formic acid, acetic acid, phthalic acid and maleic acid; and nitrogen-containing compounds such as acetonitrile, acrylonitrile, trimethylamine, triethylamine, aniline and pyridine.
【００１５】[0015]
【実施例】以下に実施例によりさらに詳細に本発明を説
明するが、本発明はこれに限定されるものではない。 （実施例１） （前段触媒）前段触媒を以下に示す方法で調製した。１
０重量％アンモニア水７００リットルにスノーテックス
−２０（日産化学（株）製シリカゾル、約２０重量％の
ＳｉＯ2含有）２１．３ｋｇを加え、撹拌、混合した
後、硫酸チタニルの硫酸溶液（ＴｉＯ2として１２５ｇ
／リットル、硫酸濃度５５０ｇ／リットル）３４０リッ
トルを撹拌しながら徐々に滴下した。得られたゲルを３
時間放置した後、ろ過、水洗し、続いて１５０℃で１０
時間乾燥した。これを５００℃で焼成し、さらにハンマ
ーミルを用いて粉砕し、分級機で分級して平均粒子径１
０μｍの粉体を得た。得られた粉体の組成は、ＴｉＯ2
−ＳｉＯ2＝８．５：１．５（モル比）であり、粉体の
Ｘ線回折チャートではＴｉＯ2やＳｉＯ2の明らかな固有
ピークは認められず、ブロードな回折ピークによって非
晶質な微細構造を有するチタンとケイ素の複合酸化物で
あることが確認された。このようにして得られた粉体を
ＴＳ−１とする。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Example 1) (Pre-stage catalyst) A pre-stage catalyst was prepared by the following method. 1
To 700 liters of 0% by weight ammonia water, 21.3 kg of Snowtex-20 (silica sol manufactured by Nissan Chemical Co., Ltd., containing about 20% by weight of SiO 2 ) was added, stirred and mixed, and then a sulfuric acid solution of titanyl sulfate (TiO 2 125g as
(340 g / l, sulfuric acid concentration: 550 g / l) were gradually added dropwise with stirring. Gel 3
After standing for hours, filtration, washing with water,
Dried for hours. This was calcined at 500 ° C., further pulverized using a hammer mill, and classified using a classifier to obtain an average particle diameter of 1: 1.
A powder of 0 μm was obtained. The composition of the obtained powder is TiO 2
—SiO 2 = 8.5: 1.5 (molar ratio), and no clear characteristic peak of TiO 2 or SiO 2 was observed in the X-ray diffraction chart of the powder, and the powder was amorphous due to a broad diffraction peak. It was confirmed that it was a composite oxide of titanium and silicon having a fine structure. The powder thus obtained is referred to as TS-1.
【００１６】上記ＴＳ−１粉体２０ｋｇにメタバナジン
酸アンモニウム０．８６ｋｇおよびパラタングステン酸
アンモニウム１．７９ｋｇを含む１０重量％モノエタノ
ールアミン水溶液１２ｋｇを加え、更に成形助剤として
の澱粉を加えて混合し、ニーダーで練り合わせた後、押
出成形機で外形１５０ｍｍ角、長さ５００ｍｍ、目開き
２．８ｍｍ、肉厚０．５ｍｍのハニカム状に成形した。
その後８０℃で乾燥した後、４５０℃で５時間焼成し
た。この成形体を硝酸パラジウムと硝酸ロジウムの混合
水溶液（Ｐｄとして４．３ｇ／リットル、Ｒｈとして
４．８ｇ／リットル含有）に含浸し、その後１５０℃で
３時間乾燥し、続いて空気雰囲気下で５００℃で２時間
焼成した。To 20 kg of the above TS-1 powder, 12 kg of a 10% by weight aqueous solution of monoethanolamine containing 0.86 kg of ammonium metavanadate and 1.79 kg of ammonium paratungstate are added, and starch as a molding aid is further added and mixed. After kneading with a kneader, the extruder was formed into a honeycomb shape having an outer shape of 150 mm square, a length of 500 mm, an aperture of 2.8 mm, and a wall thickness of 0.5 mm.
Then, after drying at 80 ° C., it was baked at 450 ° C. for 5 hours. This compact was impregnated with a mixed aqueous solution of palladium nitrate and rhodium nitrate (containing 4.3 g / L as Pd and 4.8 g / L as Rh), dried at 150 ° C. for 3 hours, and subsequently dried under air atmosphere for 500 hours. Calcination was performed at 2 ° C. for 2 hours.
【００１７】こうして得られた触媒の組成は重量百分率
で、ＴｉＯ2−ＳｉＯ2複合酸化物：Ｖ2Ｏ5：ＷＯ3：Ｐ
ｄ：Ｒｈ＝８９．６：３．０：７．０：０．２：０．２
であり、平均細孔径０．０２５μｍ、全細孔容積０．４
５ｍｌ／ｇ、ＢＥＴ比表面積１２０ｍ2／ｇであった。 （後段触媒）後段触媒を以下に示す方法で調製した。水
８０リットルに四塩化チタン（ＴｉＣｌ4）１２．８ｋ
ｇを氷冷かつ撹拌下に徐々に滴下して溶解し、この水溶
液にメタタングステン酸アンモニウム水溶液（酸化タン
グステンとして５０重量％含有）１．２ｋｇを加えた。
得られた水溶液を温度約３０℃に保持しつつ、よく撹拌
しながら、アンモニア水をｐＨが６となるまで加え、さ
らにそのまま放置して２時間熟成した。このようにして
得られたチタン−タングステン沈澱物を水洗して、１５
０℃で乾燥した後、６００℃で５時間焼成して、酸化チ
タン／酸化タングステン＝９０／１０（重量比）のチタ
ン−タングステン酸化物を得た。このようにして得られ
た粉体をＴＷ−１とする。The composition of the catalyst thus obtained is expressed in terms of percentage by weight, TiO 2 —SiO 2 composite oxide: V 2 O 5 : WO 3 : P
d: Rh = 89.6: 3.0: 7.0: 0.2: 0.2
And an average pore diameter of 0.025 μm and a total pore volume of 0.4
It was 5 ml / g and the BET specific surface area was 120 m 2 / g. (Latter-stage catalyst) A latter-stage catalyst was prepared by the following method. 12.8k of titanium tetrachloride (TiCl 4 ) in 80 liters of water
g of ice-cooled and gradually stirred to dissolve, and 1.2 kg of an aqueous solution of ammonium metatungstate (containing 50% by weight as tungsten oxide) was added to the aqueous solution.
While keeping the obtained aqueous solution at a temperature of about 30 ° C., ammonia water was added thereto until the pH reached 6, with sufficient stirring, and the mixture was left to ripen for 2 hours. The titanium-tungsten precipitate thus obtained was washed with water,
After drying at 0 ° C., it was baked at 600 ° C. for 5 hours to obtain a titanium-tungsten oxide of titanium oxide / tungsten oxide = 90/10 (weight ratio). The powder thus obtained is designated as TW-1.
【００１８】このようにして得られた共沈チタン−タン
グステン酸化物粉体２０ｋｇにメタバナジン酸アンモニ
ウム１．４ｋｇ、シュウ酸１．７ｋｇおよびモノエタノ
ールアミン０．４ｋｇを水５リットルに溶解させた溶液
を加え、さらにフェノール樹脂（ベルパール（商品
名）、カネボウ（株）製）１ｋｇと成形助剤としての澱
粉０．５ｋｇとを加えて混合しニーダーで混練りした
後、押出成形機で外形１５０ｍｍ角、長さ５００ｍｍ、
目開き２．８ｍｍ、肉厚０．５ｍｍのハニカム状に成形
した。その後８０℃で乾燥した後、４５０℃で５時間焼
成した。こうして得られた触媒の組成は重量百分率で、
Ｖ2Ｏ5：ＷＯ3：ＴｉＯ2＝５：１０：８５であり、全細
孔容積は０．３７ｍｌ／ｇであり、第一細孔群（０．０
１〜０．０５μｍの範囲に孔径分布ピークを有する細孔
群）および第二細孔群（０．１〜０．８μｍの範囲に孔
径分布ピークを有する細孔群）はそれぞれ全細孔容積の
５７％および３７％であった。また、ＢＥＴ比表面積７
８ｍ2／ｇであった。A solution prepared by dissolving 1.4 kg of ammonium metavanadate, 1.7 kg of oxalic acid and 0.4 kg of monoethanolamine in 5 l of water was added to 20 kg of the coprecipitated titanium-tungsten oxide powder thus obtained. In addition, 1 kg of a phenolic resin (Bellpearl (trade name), manufactured by Kanebo Co., Ltd.) and 0.5 kg of starch as a molding aid are added, mixed and kneaded with a kneader. Length 500mm,
It was formed into a honeycomb shape having a mesh size of 2.8 mm and a wall thickness of 0.5 mm. Then, after drying at 80 ° C., it was baked at 450 ° C. for 5 hours. The composition of the catalyst thus obtained is in weight percentage,
V 2 O 5 : WO 3 : TiO 2 = 5: 10: 85, the total pore volume was 0.37 ml / g, and the first pore group (0.0
The group of pores having a pore size distribution peak in the range of 1 to 0.05 μm) and the second group of pores (pore groups having a pore size distribution peak in the range of 0.1 to 0.8 μm) each have a total pore volume. 57% and 37%. In addition, BET specific surface area 7
It was 8 m 2 / g.
【００１９】（試験条件）前段触媒を前段反応器に、後
段触媒を後段反応器に充填し、前段反応器と後段反応器
の間に熱交換器を設置し、後段反応器入口温度を低下さ
せるようにした。以下に反応条件を示す。 前段反応器入口温度：４００℃ 前段触媒空間速度（ＳＴＰ）：３０００ｈｒ-1 後段反応器入口温度：２５０℃ 後段触媒空間速度（ＳＴＰ）：３０００ｈｒ-1 ガス組成：塩化ビニルモノマー（ＶＣＭ）１０００ｐｐ
ｍ、塩化ビニリデン（ＶＤＣ）５００ｐｐｍ、空気バラ
ンス 結果を表１に示す。(Test conditions) The first-stage catalyst is charged into the first-stage reactor, the second-stage catalyst is charged into the second-stage reactor, and a heat exchanger is installed between the first-stage reactor and the second-stage reactor to lower the inlet temperature of the second-stage reactor. I did it. The reaction conditions are shown below. Preceding reactor inlet temperature: 400 ° C. precatalyst space velocity (STP): 3000 hr -1 subsequent reactor inlet temperature: 250 ° C. stage catalyst space velocity (STP): 3000 hr -1 gas composition: Vinyl chloride monomer (VCM) 1000PP
m, vinylidene chloride (VDC) 500 ppm, air balance The results are shown in Table 1.
【００２０】（比較例１）実施例１における後段触媒を
設置しない処理方法、すなわち前段触媒のみで処理を行
った。反応条件は実施例１と同じとした。結果を表１に
示す。(Comparative Example 1) The treatment method in Example 1 without the latter-stage catalyst, ie, the treatment was performed only with the former-stage catalyst. The reaction conditions were the same as in Example 1. Table 1 shows the results.
【００２１】[0021]
【表１】 [Table 1]
【００２２】（実施例２） （前段触媒）前段触媒を以下に示す方法で調製した。
１．４ｍｍ角の孔径を持つコージェライトハニカム担体
にγ−Ａｌ2Ｏ3とＣｅＯ2（γ−Ａｌ2Ｏ3／ ＣｅＯ2＝
１０／１（重量比））をコーティングした後、２００℃
で２時間乾燥し、その後空気流通下で５００℃で３時間
焼成した。担持量は担体１リットル当たり９０ｇであっ
た。この担体を硝酸パラジウム水溶液（Ｐｄとして１８
ｇ／リットル）に含浸し１５０℃で２時間乾燥し、その
後４００℃で２時間Ｈ2還元（Ｈ2５％、Ｎ2９５％）
し、前段触媒を得た。Ｐｄの担持量は触媒１リットル当
たり２．０ｇであった。Example 2 (Pre-Catalyst) A pre-catalyst was prepared by the following method.
Γ-Al 2 O 3 and CeO 2 (γ-Al 2 O 3 / CeO 2 =
10/1 (weight ratio)) and then 200 ° C
For 2 hours, and then calcined at 500 ° C. for 3 hours under flowing air. The supported amount was 90 g per liter of the carrier. This carrier is treated with an aqueous solution of palladium nitrate (18% as Pd).
g / liter), dried at 150 ° C. for 2 hours, and then reduced at 400 ° C. for 2 hours with H 2 (H 2 5%, N 2 95%).
Then, a pre-stage catalyst was obtained. The supported amount of Pd was 2.0 g per liter of the catalyst.
【００２３】（後段触媒）後段触媒を以下に示す方法で
調製した。実施例１の前段触媒のＴＳ−１と同様に調製
したＴｉＯ2−ＳｉＯ2複合酸化物粉体１２ｋｇと実施例
１の後段触媒のＴＷ−１と同様に調製した共沈チタン−
タングステン酸化物粉体８ｋｇとにメタバナジン酸アン
モニウム１．４ｋｇ、シュウ酸１．７ｋｇおよびモノエ
タノールアミン０．４ｋｇを水５リットルに溶解させた
溶液を加え、さらにフェノール樹脂（ベルパール（商品
名）、カネボウ（株）製）１ｋｇと成形助剤としての澱
粉０．５ｋｇとを加えて混合しニーダーで混練りした
後、押出成形機で外形１５０ｍｍ角、長さ５００ｍｍ、
目開き２．８ｍｍ、肉厚０．５ｍｍのハニカム状に成形
した。その後８０℃で乾燥した後、４５０℃で５時間焼
成した。(Late-stage catalyst) A late-stage catalyst was prepared by the following method. 12 kg of the TiO 2 —SiO 2 composite oxide powder prepared in the same manner as the first stage catalyst TS-1 in Example 1 and the coprecipitated titanium powder prepared in the same manner as the second stage catalyst TW-1 in Example 1
A solution of 1.4 kg of ammonium metavanadate, 1.7 kg of oxalic acid and 0.4 kg of monoethanolamine dissolved in 5 liters of water was added to 8 kg of tungsten oxide powder, and phenol resin (Bellpearl (trade name), Kanebo) 1 kg and 0.5 kg of starch as a molding aid were added, mixed, kneaded with a kneader, and then extruded with a 150 mm square, 500 mm long by an extruder.
It was formed into a honeycomb shape having a mesh size of 2.8 mm and a wall thickness of 0.5 mm. Then, after drying at 80 ° C., it was baked at 450 ° C. for 5 hours.
【００２４】こうして得られた触媒の組成は重量百分率
で、Ｖ2Ｏ5：ＷＯ3：ＴｉＯ2：ＴｉＯ2−ＳｉＯ2複合酸
化物＝５：６：３２：５７であり、全細孔容積は０．３
２ｍｌ／ｇであり、第一細孔群（０．０１〜０．０５μ
ｍの範囲に孔径分布ピークを有する細孔群）および第二
細孔群（０．１〜０．８μｍの範囲に孔径分布ピークを
有する細孔群）はそれぞれ全細孔容積の５８％および３
１％であった。また、ＢＥＴ比表面積１０２ｍ2／ｇで
あった。 （試験条件）前段触媒を前段反応器に、後段触媒を後段
反応器に充填し、前段反応器と後段反応器の間に熱交換
器を設置し、後段反応器入口温度を低下させるようにし
た。以下に反応条件を示す。The composition of the catalyst thus obtained was expressed as a percentage by weight, V 2 O 5 : WO 3 : TiO 2 : TiO 2 —SiO 2 composite oxide = 5: 6: 32: 57, and the total pore volume was 0.3
2 ml / g, the first pore group (0.01 to 0.05 μ
m) and the second group of pores (pore group having a pore size distribution peak in the range of 0.1 to 0.8 μm) are 58% and 3% of the total pore volume, respectively.
1%. The BET specific surface area was 102 m 2 / g. (Test conditions) The first-stage catalyst was charged into the first-stage reactor, the second-stage catalyst was charged into the second-stage reactor, and a heat exchanger was installed between the first-stage reactor and the second-stage reactor to lower the inlet temperature of the second-stage reactor. . The reaction conditions are shown below.
【００２５】前段反応器入口温度：３５０℃ 前段触媒空間速度（ＳＴＰ）：１０，０００ｈｒ-1 後段反応器入口温度：２５０℃ 後段触媒空間速度（ＳＴＰ）：３０００ｈｒ-1 ガス組成：塩化メチレン４００ｐｐｍ、メタノール８０
００ｐｐｍ、空気バランス 結果を表２に示す。 （比較例２）実施例２における後段触媒を設置しない処
理方法、すなわち前段触媒のみで処理を行った。反応条
件は実施例２と同じとした。結果を表２に示す。The preceding reactor inlet temperature: 350 ° C. precatalyst space velocity (STP): 10,000 -1 subsequent reactor inlet temperature: 250 ° C. stage catalyst space velocity (STP): 3000 hr -1 gas composition: methylene chloride 400 ppm, Methanol 80
00 ppm, air balance The results are shown in Table 2. (Comparative Example 2) The treatment method in Example 2 without the latter catalyst, that is, the treatment was performed only with the former catalyst. The reaction conditions were the same as in Example 2. Table 2 shows the results.
【００２６】[0026]
【表２】 [Table 2]
【００２７】（実施例３） （前段触媒）前段触媒を以下に示す方法で調製した。
１．４ｍｍ角の孔径を持つコージェライトハニカム担体
に、実施例１の前段触媒のＴＳ−１と同様に調製したＴ
Ｓ−１粉体とＳｉＯ2（ＴＳ−１／ＳｉＯ2＝３／２（重
量比））をコーティングした後、２００℃で２時間乾燥
し、その後空気流通下で５００℃で３時間焼成した。担
持量は担体１リットル当たり９０ｇであった。この担体
を硝酸パラジウムと硝酸白金の混合水溶液（Ｐｄとして
８ｇ／リットル、Ｐｔとして１６ｇ／リットル）に含浸
し、１５０℃で２時間乾燥し、その後４００℃で２時間
Ｈ2還元（Ｈ2５％、Ｎ2９５％）し、前段触媒を得た。
ＰｄおよびＰｔの担持量は触媒１リットル当たり各々
０．８ｇ、１．７ｇであった。Example 3 (Pre-Catalyst) A pre-catalyst was prepared by the following method.
A cordierite honeycomb support having a pore size of 1.4 mm square was filled with T prepared in the same manner as the pre-stage catalyst TS-1 of Example 1.
After coating the S-1 powder with SiO 2 (TS-1 / SiO 2 = 3/2 (weight ratio)), it was dried at 200 ° C. for 2 hours and then calcined at 500 ° C. for 3 hours under flowing air. The supported amount was 90 g per liter of the carrier. The carrier is impregnated with a mixed aqueous solution of palladium nitrate and platinum nitrate (8 g / l as Pd, 16 g / l as Pt), dried at 150 ° C. for 2 hours, and then reduced at 400 ° C. for 2 hours with H 2 (H 2 5% , N 2 95%) to obtain a first-stage catalyst.
The supported amounts of Pd and Pt were 0.8 g and 1.7 g, respectively, per liter of the catalyst.
【００２８】（後段触媒）実施例２の後段触媒と同じ触
媒を使用した。 （試験条件）前段触媒を前段反応器に、後段触媒を後段
反応器に充填し、前段反応器と後段反応器の間に熱交換
器を設置し、後段反応器入口温度を低下させるようにし
た。以下に反応条件を示す。 前段反応器入口温度：３５０℃ 前段触媒空間速度（ＳＴＰ）：１０，０００ｈｒ-1 後段反応器入口温度：２５０℃ 後段触媒空間速度（ＳＴＰ）：３０００ｈｒ-1 ガス組成：ベンゼン１００ｐｐｍ、塩化水素（ＨＣｌ）
１００ｐｐｍ、空気バランス 結果を表３に示す。(Second stage catalyst) The same catalyst as the second stage catalyst of Example 2 was used. (Test conditions) The first-stage catalyst was charged into the first-stage reactor, the second-stage catalyst was charged into the second-stage reactor, and a heat exchanger was installed between the first-stage reactor and the second-stage reactor to lower the inlet temperature of the second-stage reactor. . The reaction conditions are shown below. Front reactor inlet temperature: 350 ° C. Front catalyst space velocity (STP): 10,000 hr −1 Rear reactor inlet temperature: 250 ° C. Rear catalyst space velocity (STP): 3000 hr −1 Gas composition: 100 ppm benzene, hydrogen chloride (HCl) )
100 ppm, air balance The results are shown in Table 3.
【００２９】（比較例３）実施例３における後段触媒を
設置しない処理方法、すなわち前段触媒のみで処理を行
った。反応条件は実施例３と同じとした。結果を表２に
示す。(Comparative Example 3) The treatment method in Example 3 without the latter-stage catalyst, that is, the treatment was performed only with the former-stage catalyst. The reaction conditions were the same as in Example 3. Table 2 shows the results.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【発明の効果】本発明によると、有機ハロゲン化合物を
含有する排ガス、または、無機ハロゲン化合物と有機物
とを含有する排ガスを処理するに際し、排ガス中に含ま
れる有機ハロゲン化合物や有機物を効率良く処理すると
ともに、副生成物、特にダイオキシン類を充分に低減す
る方法を提供するAccording to the present invention, when treating an exhaust gas containing an organic halogen compound or an exhaust gas containing an inorganic halogen compound and an organic substance, the organic halogen compound or the organic substance contained in the exhaust gas is efficiently treated. And a method for sufficiently reducing by-products, particularly dioxins.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 23/652 Ｂ０１Ｊ 23/64 １０３Ａ (72)発明者 池田 光明 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 (72)発明者 森田 敦 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 (72)発明者 岡村 敦志 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 Ｆターム(参考） 4D048 AA11 AB03 BA03X BA06X BA07X BA08Y BA10X BA19X BA23X BA25Y BA26Y BA27X BA28Y BA30X BA31X BA32Y BA33X BA35Y BA41X BA42X BB02 CC32 CC46 CC54 DA03 DA05 DA13 4G069 AA03 AA08 BA01A BA01B BA02A BA02B BA04A BA04B BA05A BA13B BA20A BA20B BB02A BB02B BB04A BB04B BB06A BB06B BC31A BC43A BC43B BC54A BC54B BC58A BC59A BC60A BC60B BC62A BC70A BC71A BC71B BC72A BC72B BC75A BC75B CA10 CA11 CA19 DA05 EA19 EB12Y EB14Y EB15Y EC02Y EC03Y EC07Y EC15Y EC17Y EC20 EE09 FA01 FB67 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 23/652 B01J 23/64 103A (72) Inventor Mitsuaki Ikeda 992, Okihama, Nishioki, Aboshi-ku, Himeji-shi, Hyogo Nippon Shokubai Co., Ltd. (72) Inventor Atsushi Morita 992, Okihama-shi Nishioki, Himeji-shi, Hyogo Prefecture Nippon Shokubai Co., Ltd. F term (for reference) 4D048 AA11 AB03 BA03X BA06X BA07X BA08Y BA10X BA19X BA23X BA25Y BA26Y BA27X BA28Y BA30X BA31X BA32Y BA33X BA35Y BA41X BA42X BB02 BA32 BA02 BA01 BA02 BA02 BA02 BA01 BA02 BA02 BA01 BB04B BB06A BB06B BC31A BC43A BC43B BC54A BC54B BC58A BC59A BC60A BC60B BC 62A BC70A BC71A BC71B BC72A BC72B BC75A BC75B CA10 CA11 CA19 DA05 EA19 EB12Y EB14Y EB15Y EC02Y EC03Y EC07Y EC15Y EC17Y EC20 EE09 FA01 FB67
Claims (5)
または、無機ハロゲン化合物と有機物とを含有する排ガ
スを処理する方法において、ガス流れ方向に、前段触媒
と後段触媒を配置し、後段触媒層の入口温度を３００℃
以下とすることを特徴とする排ガスの処理方法。An exhaust gas containing an organic halogen compound,
Alternatively, in a method for treating an exhaust gas containing an inorganic halogen compound and an organic substance, a front catalyst and a rear catalyst are arranged in a gas flow direction, and an inlet temperature of the rear catalyst layer is set to 300 ° C.
An exhaust gas treatment method characterized by the following.
または、無機ハロゲン化合物と有機物とを含有する排ガ
スを処理する方法において、ガス流れ方向に、前段触媒
として有機ハロゲン化合物分解触媒を、後段触媒として
ダイオキシン分解触媒を配置することを特徴とする排ガ
スの処理方法。2. Exhaust gas containing an organic halogen compound,
Alternatively, in the method for treating an exhaust gas containing an inorganic halogen compound and an organic substance, an exhaust gas treatment characterized by disposing an organic halogen compound decomposition catalyst as a first-stage catalyst and a dioxin decomposition catalyst as a second-stage catalyst in a gas flow direction. Method.
填し、かつ前段反応器と後段反応器との間に熱交換器を
設置する、請求項１または２記載の排ガスの処理方法。3. The method for treating exhaust gas according to claim 1, wherein the first-stage catalyst and the second-stage catalyst are charged into separate reactors, and a heat exchanger is provided between the first-stage reactor and the second-stage reactor.
ｉ、Ｓｉ、Ｚｒ、ＣｅおよびＷから選ばれる少なくとも
１種の元素の酸化物を、Ｂ成分として、Ｖ、Ｃｕ、Ｃ
ｒ、Ｍｎ、Ｐｄ、Ｒｈ、Ｐｔ、Ｒｕから選ばれる少なく
とも１種の元素の金属または酸化物を含有するものであ
り、後段触媒が、Ｔｉ、Ｗ、ＭｏおよびＶから選ばれる
少なくとも１種の元素の酸化物を含有するものである、
請求項１から３のいずれかに記載の排ガスの処理方法。4. The pre-catalyst comprises Al, T as an A component.
An oxide of at least one element selected from i, Si, Zr, Ce and W is used as a B component, and V, Cu, C
r, Mn, Pd, Rh, Pt, and Ru, containing a metal or oxide of at least one element selected from the group consisting of at least one element selected from Ti, W, Mo, and V Containing an oxide of
The method for treating exhaust gas according to claim 1.
℃、空間速度を５００〜５０，０００ｈｒ-1とし、後段
触媒層の入口温度を１００〜３００℃、空間速度を２０
０〜５０，０００ｈｒ-1とする、請求項４記載の排ガス
の処理方法。5. An inlet temperature of the pre-stage catalyst layer is set to 150 to 500.
° C, the space velocity is 500-50,000 hr -1 , the inlet temperature of the latter catalyst layer is 100-300 ° C, and the space velocity is 20.
The method for treating exhaust gas according to claim 4, wherein the treatment time is from 0 to 50,000 hr -1 .
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|---|---|---|---|
| JP2000063863A JP2001246230A (en) | 2000-03-08 | 2000-03-08 | Exhaust gas treatment method |
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|---|---|---|---|---|
| WO2007037026A1 (en) * | 2005-09-28 | 2007-04-05 | Nippon Oil Corporation | Catalyst and process for producing the same |
| WO2008041756A1 (en) * | 2006-10-05 | 2008-04-10 | Nippon Shokubai Co., Ltd. | Catalyst for treating an exhaust gas containing organic acid, and method for treating an exhaust gas containing organic acid |
| JP2008246437A (en) * | 2007-03-30 | 2008-10-16 | Tokuyama Corp | Treatment method of halogenated aliphatic hydrocarbon-containing gas |
| JP2009136841A (en) * | 2007-12-10 | 2009-06-25 | Chubu Electric Power Co Inc | Catalyst oxidation treatment device and catalyst oxidation treatment method |
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2000
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037026A1 (en) * | 2005-09-28 | 2007-04-05 | Nippon Oil Corporation | Catalyst and process for producing the same |
| US8222173B2 (en) | 2005-09-28 | 2012-07-17 | Nippon Oil Corporation | Catalyst and method of manufacturing the same |
| JP5067942B2 (en) * | 2005-09-28 | 2012-11-07 | Ｊｘ日鉱日石エネルギー株式会社 | Catalyst and method for producing the same |
| WO2008041756A1 (en) * | 2006-10-05 | 2008-04-10 | Nippon Shokubai Co., Ltd. | Catalyst for treating an exhaust gas containing organic acid, and method for treating an exhaust gas containing organic acid |
| JP2010505600A (en) * | 2006-10-05 | 2010-02-25 | 株式会社日本触媒 | Catalyst for treating exhaust gas containing organic acid and method for treating exhaust gas containing organic acid |
| JP2008246437A (en) * | 2007-03-30 | 2008-10-16 | Tokuyama Corp | Treatment method of halogenated aliphatic hydrocarbon-containing gas |
| JP2009136841A (en) * | 2007-12-10 | 2009-06-25 | Chubu Electric Power Co Inc | Catalyst oxidation treatment device and catalyst oxidation treatment method |
| KR20220148476A (en) | 2021-04-29 | 2022-11-07 | 주식회사 엘지화학 | Method for decomposing of waste |
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